EP0127084A1

EP0127084A1 - Polyacetal resin composition

Info

Publication number: EP0127084A1
Application number: EP84105647A
Authority: EP
Inventors: Takuzo Kasuga; Yukio Ikenaga; Masami Yamawaki; Keizo Tanimura
Original assignee: Polyplastics Co Ltd
Current assignee: Polyplastics Co Ltd
Priority date: 1983-05-25
Filing date: 1984-05-17
Publication date: 1984-12-05
Also published as: JPS59217751A; JPH0211624B2; CA1270085A; DE3462264D1; EP0127084B1; US4596847A

Abstract

A polyacetal resin composition comprises polyactal resin, carbon black and a polypropylene giycol/polyethylene glycol ether copolymer. It is improved in the antistatic property, the stability to heat and mechanical properties.

Description

The present invention relates to a polyacetal resin composition containing carbon black, which has excellent mechanical properties, thermal stability and moldability.
The compounding of carbon black into polyacetal resin has hitherto been practiced not only for the purpose of mere coloration but also for use of this resin as sliding parts, covering parts or the like, by providing the resin with electric conductivity and weatherability. However, addition of a sufficient amount of carbon black to impart the desired performance to the polyacetal resin sometimes brings about notable hindrance to the mechanical properties and moldability of the polyacetal resin and degradation of the heat stability.
The present invention has been accomplished as a result of earnest studies with attention focused on such disadvantages and relates to a polyacetal resin composition improved with regard to the aforementioned disadvantages by addition of polypropylene glycol/ polyethylene glycol ether copolymer to the polyacetal resin composition coataining carbon black.
The carbon black used in this invention is appropriately selected according to the purposes, e.g., for imparting electric conductivity and weatherability to polyacetal resin or for colorations. Thus, for the purpose of imparting electric conductivity, carbon black which has a developed structure, small particle diameters, high porosity and a large surface area is suitable. As such carbon black, electrically conductive furnace black, acetylene black, etc. is preferable. For the purpose of inhibition against deterioration or coloration, furnace and channel blacks are adequate, but besides them thermal black, etc. may be utilized according to the uses of the resin. As the carbon black used according to this invention, any of the above-mentioned carbon blacks is usable. The amount of carbon black'added may be appropriately selected according to the object, the desirable range being 0.1 to 30 weight % of the total composition. With less than 0.1 weight % of carbon black, it is difficult to achieve the required object, while with more than 30 weight %, its incorporation into the polyacetal resin as well as extrusion becomes difficult. The amount of its addition desirable from the aspect of physical properties and compounding is in the range of 0.5 to 10 weight % of the total composition.
The polypropylene glycol/polyethylene glycol ether copolymer according to this invention is a high molecular nonionic surfactant having polypropylene glycol radical as a hydrophobic radical and polyethylene glycol radical as a hydrophilic radical. The surfactant may have hydrophobic and hydrophilic radicals with their molecular weights altered according to objects, the mean molecular weight of the hydrophobic radical preferably being 1,000 to 2,000 as against the molecular weight of 1,300 to 15,000 of the nonionic surfactant. Addition of polypropylene glycol/polyethylene glycol ether copolymer to the polyacetal resin containing carbon black causes better dispersion of the carbon black into the resin, resulting in enhanced melt fluidity, improved thermal stability and ameliorated moldability. Moreover, such excellent characteristics as lowered volume resistivity, improved mechanical properties, particularly elongation and impact resistance,^-may be achieved. A preferable amount of polypropylene glycol/polyethylene glycol ether copolymer to be added should be 0.1 to 10 weight %, more preferably, 1 to 5 weight %, of the total resin composition. With its increasing addition, the melt fluidity, elongation, impact resistance, etc. may be improved, but an addition over 30 weight % which will cause lowering of the tensile strength is not appropriate.
According to this invention, the polyacetal resin composition may be one further compounded with an amide compound. In that way, the thermal stability will be further improved.
The amide compound used according to this invention includes mono- or polycarboxylic acid amide compounds represented by the following general formula and ethylene oxide adducts thereof:
wherein R represents a carboxylic acid residue which is a saturated or unsaturated hydrocarbon radical having 2 or more carbon atoms, especially those with 2 to 23 carbon atoms being preferable, or R may be a radical representing a fundamental unit of a vinyl polymer or copolymer, n is an integer of 1 or above, preferably 1 to 6, and x and y are each 0 or an integer of 1 or above, preferably 1 to 10.
The amide compounds used according to this invention include those of fatty acids, higher fatty acids, etc. or ethylene oxide adducts thereof, and those of polymers of vinyl compounds or copolymers containing vinyl compounds as major components or ethylene oxide adducts thereof. Examples of the amide compounds are butyramide, caproamide, caprylamide, capramide, lauramide, myristamide, palmitamide, stearamide, behenamide, ole- amide, linolamide, linolenamide, erucamide, a natural higher fatty acid amide as a mixture of higher fatty acid amides, succinamide, adipamide, sebacamide, dodecanedicarboxyamide, 1,6-cyclohexanedicarbodyamide, propane-1,2,3-tricarboxyamide, benzamide, phthalamide, terephtha amide, trimellitamide, pyromellitamide, polyacrylamide, polymethacrylamide, ethylene/acrylamide copolymer, and ethylene oxide adducts thereof. These amide compounds may be used alone or in combination of two or more of them. Preferable amide compounds are ethylene oxide adducts of higher fatty acid amides, especially those with the mol number of ethylene oxide added (x + y) of 2 to 7 showing a prominent effect. The addition of these amide compounds should be 0.1 to 1.5 weight %, preferably 0.3 to 5 weight % of the total polyacetal resin composition.
The polyacetal used according to this invention is polyoxymethylene homopolymer or polyacetal copolymer with most of its main chain composed of oxymethylene chains. In these polyacetal resins, well-known antioxidants, acid resisting agents and the like additives may be compounded. Examples of the antioxidants are phenols such as 2,2'-methylenebis(4-methyl-6-t-butyl phenol), hexamethylene glgcol bis(3,5-di-t-butyl-4-hydroxyhydrocinnamate), tetrakis [methylene (3,5-dit-butyl-4-hydroxyhydrocinnamate)] methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) benzene, 4,4'-methylenebis(2,6-di-t-butylphenol) and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate and amines such as N-phenyl-N'-isopropyl- p-phenylenediamine, N,N'-diphengl-p-phenylenediamine, 4,4'-bis(4-d,d-dimethylbenzyl)diphenylamine, a condensate of diphenylamine with acetone, N-phenyl-p-naphthylamine and N,N'-di-β-naphthyl-p-phenylenediamine. Examples of acid.resisting agents are urea, dicyandiamide, melamine, polyamide, alkali or alkaline earth metal salts of lower and higher fatty acids, e.g., calcium stearate, hydroxides, inorganic salts, alkoxides, etc. of alkali or alkaline earth metals. These antioxidants and acid resisting agents may be used alone or in combinations of two or more of them.
When stearamide, lauric acid diethanolamide, etc. are used as amide compounds, the resin composition of this invention in which alkyl-substituted diphenylamine, etc. are incorporated therewith as antioxidants for amines give an especially excellent heat stabilizing effect.
With the polyacetal resin composition of this invention, well-known weathering stabilizer, e.g., ultraviolet ray stabilizer or photostabilizer, may be used. Examples of such agents include ultraviolet ray stabilizers such as salicylate compounds, benzophenone compounds or benzotriazole compounds, and photostabilizers such as hindered amines.
In practicing this invention, joint use, in addition to the additives mentioned above, of additives which further improve dispersion of carbon black, e.g., oligomers, is recommended. Oligomers are polymers having low molecular weights which themselves are lacking in moldability, and they should preferably be solid at normal temperature for convenience in addition operation. As examples, there may be mentioned paraffin wax, microcrystalline wax, and polyolefin waxes such as polyethylene wax or polypropylene wax. As a polyethylene wax, those manufactured by thermal decomposition of high-pressure polyethylene resin of a high molecular weight, or by direct polymerization of an ethylene monomer is usable. Generally, polyethylene wax having its molecular weight lowered by thermal decomposition at a high temperature of 300°C or above contains branches and polar radicals, so that is is especially preferable in regard to dispersibility, etc. to polyethylene mainly composed of hydrocarbons obtained by direct polymerization process. An example of other well-known carbon black dispersants is oil. The dispersants may be used as a m.'.xture of two or more of them. They further improve heat stability and moldability, because they enhance dispersion of carbon black, enabling a polyacetal resin to be obtained with uniform and stable mechalical properties. The desirable amount of polyolefin wa es such as the aforementioned polyethylene_.wax should be 0.3 to 3 weight %, preferably 0.5 to 2 weight % of the resin composition.
Among the composition of this invention constituted as mentioned above, those containing electrically conductive carbon black for the purpose of improvement in electrical conductivity enables reduction of the amount of addition for cost advantage, because only a small amount of carbon black added provides for excellent electrical properties.
The composition according to the invention provides a resulting, moulded article with the antistatic property, improved resistance to abrasion and improved durability. Thereafter the article is suitable for parts of electric instruments, motor cars and other instruments, such as a rotatable member, a shaft-bearing member and a slidable member. For example of these applications, the invention applies to parts of audio tape recorders and video tape recorders, such as a gear, a cam, a lever, a guiding member and a clatch. It also applies to parts of a tape cassette, such as a guiding member, a roller, a post, a ball and a pin, which come in sliding contact with running tape.
In a video tape recorder, parts thereof have been made of metal material, therefore through complicated manufacturing steps such as processing of metal pieces and surface polishing. That has had disadvantageous influence on the manufacturing and eventually products are expensive.
Moreover plastic material has been seeked in the way of material instead of metal. But it is easy to be charged electrostaticcally while being in contact with running tape. Therefor contaminants in air happen to attach to the tape and the electrostatic charge disturbs the video image. Further it is seen that plastic parts and the surface of tape are abraded, whereby to damage the image properties. Also tape is difficult to run because of bad friction property. The electrostatic charge produces noises in recording and playing of souhd.
In order to solve those problems, the composition according to the invention is the most suitable as plastic material, having the antistatic property, being improved in mechanical properties, friction property and abrasion property.
The invention applies also to a rotatable member, a sliding member and other parts of mechanism of various business machines such as facsimiles, copying machines and computors and radios, cameras and fiber machines. When the invention applies to the paper feeding mechanism in facsimiles and copying machines, the electrostatic charge is not produced and paper running is improved. The invention is useful to remove the electrostatic charge which has been made during transmission of articles, for example helpful as parts of feeding pipes, inlet and outlet. This way seeding machines are improved with the invention.
The composition of this invention may be readily prepared by methods used for resins containing fillers. For example, a method of preparing pellets by kneading in and extruding the components by use of an extruder after mixing, followed by molding, a method of mixing pellets of different compositions before molding and obtaining the composition by molding and a method of directly charging the components into a molder are available.
To the polyacetal reain composition of this invention, well-known additives such as varieties of organic high molecular materials or inorganic fillers may be further added. The organic high molecular materials include, for example, polyurethane, fluororesins, vinyl polymers-and copolymers such as ethylene/vinyl acetate copolymer, ethylene/alkyl acrylate copolymer, stgrene/butadiene/acrylonitrile copolymer and styrene/acrylonitrile copolymer, a polyphase graft copolymer composed of polyacrylate resin and thermoplastic segment type copolyester. Inorganic fillers refer, for example, to glass fiber, carbon fiber, potassium titanate fiber, glass flake, mica, talc and metal foil. Besides them, antistatic agents, coloring agents, lubricants, mold releasing agents, nucleating agents, stabilizers or surface active agents may be added to provide the properties called for.
This invention will now be described in more detail with reference to embodiments and comparative examples; however, of course, this does not imply that this invention is limited to them.

Examples l'to 10 and Comparative Examples 1 and 2:

Polyacetal resin powder (Duracon, a product of Polyplastics Co., Ltd.) was mixed with electrically conductive carbon black and polypropylene glycol/polyethylene glycol ether copolymer of compositions shown in Table 1, lauric acid diethanolamide (2 weight %), and low molecular weight polyethylene wax (molecular weight 5,000, manufactured by thermal decomposition) (1 weight %) in a Henschel mixer and the mixture was melted and kneaded by use of a 28 mm two-axis extruder, thereby preparing a pellet form composition. Thereafter, test pieces were formed from this pellet using an extrusion-molder and their physical properties were measured. Measurements of the fluidity and heat stability were made of pellets per se. On the other hand, as a comparative example, similar measurements were made of a composition not containing polypropylene glycol/polyethylene glycol ether copolymer.
The values of fluidity listed are those obtained by measurements with use of a melt indexer set at 190°C. The values of heat stability refer to the rate of weight reduction by heating per minut (%/min) when a pellet is heated in air at 230⁰C for 45 minutes. Volume resistivity was calculated from resistance at both ends of a test piece coated with an electrically conductive paint on both ends thereof and dried. Tensile elongation was measured by the method of ASTM D 638 and the Izod impact strength by the method of D 256.

Example 11 and Comparative Example 3:

Polyacetal resin powder (Duracon, a product of Polyplastics Co., Ltd.) was mixed with, as in Example 1, furnace black and polypropylene glycol/polyethylene glycol ether copolymer of compositions shown in Table 2 and lauric acid diethanolamide (2 weight %). Pellets were prepared from this mixture and measurements of physical properties were made with them. As a comparative example, similar measurements were made of a composition not containing palypropylene glycol/ polyethylene glycol ether copolymer.

Example 12 and Comparative Example 4:

Polyacetal resin powder (Duracon, a product of Polyplastics Co., Ltd.) was mixed with, in the similar manner as in Example 1, polypropylene glycol/polyethylene glycol ether copolymer (3 weight %), furnace black (3 weight %) and lauric acid diethanolamide (2 weight %). From this mixture, pellets were prepared. These pieces (120 x 120 mm square, 3 mm thick) were molded from the pellets thus prepared, using a molder, and a falling weight impact test was conducted on these pieces (Table 3). The impact value is given by the 50 % breakdown energy (the impact energy when 50 % of the total number of the test pieces are broken down) as measured by using a tester of JIS K 7211.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A polyacetal resin composition which comprises polyacetal resin, carbon black and an ether copolymer of polypropylene glycol and polyethylene glycol.
2. A polyacetal resin composition according to Claim 1 wherein the content of said carbon black is 0.1 to 30 weight % of the total composition and that of said polypropylene glycol/polyethylene glycol ether copolymer is 0.1 to 10 weight % of the total resin composition.
3. A polyacetal resin composition according to Claim 1 or 2 wherein an amide compound is compounded in the polyacetal resin composition.
4. A polyacetal resin composition according to Claim 3 wherein said amide compound is one represented by the following general formula:
wherein R denotes a carboxylic acid residue; x and y are each 0 or an integer of 1 or above; and n is an integer of 1 or above.
5. A polyacetal resin composition according to Claim 4 wherein R in the general formula of the amide compound is a saturated or unsaturated hydrocarbon radical or a radical comprising a fundamental unit of a vinyl polymer or copolymer.
6. A polyacetal resin composition according to Claim 4 or 5 wherein R in the general formula of the amide compound is a saturated or unsaturated hydrocarbon radical having 2 to 23 carbon atoms.
7. A polyacetal resin composition according to any one of Claims 1 through 6 wherein a low molecular weight polyolefin wax is compounded in the composition.
8. A polyacetal resin composition according to Claim 7 wherein said low molecular weight polyolefin wax is polyethylene wax prepared by a thermal decomposition process.
9. A polyacetal resin composition according to any one of Claims 1 through 8 wherein amines are compounded in the composition as antioxidant.